Green dye and process of making same.



UNITED STATES PATENT FFICE.

OSCAR BALLY, OF MANNHEIM, GERMANY, ASSIGNOR TO THE BADISOHE ANILIN ANDSODA FABRIK, OF LUDWIGSI-IAFEN, GERMANY.

GREEN DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 631,605, dated August22, 1899.

Application filed April 12, 1899. Serial No. 712,762. (No specimens.)

To all whom it may concern.-

Be it known that I, OSCAR BALLY, doctor of philosophy, a citizen of theSwiss Republic, residing at Mannheim, in the Grand Duchy of Baden andEmpire of Germany, have invented new and useful Improvements in theManufacture of Green Coloring-Matters of the Anthracene Series, (forwhich application for patent was made in Germany, No. B 23,567, October17, 1898, and No. B 23,574, October 18, 1898,) of which the following isa specification.

In an application for patent of even date herewith, filed April 12,1899, Serial No. 712,763, I have described the production of halogenderivatives of alphylated amido-anthraquinones.

My present invention relates to the production of green coloring-mattersof the anthracene series by treating the said halogen derivatives withprimary aromatic amins.

In order to prepare my new coloring-matters, the halogen derivative isfirst heated to a high temperature with about ten times the quantity ofthe primary aromatic amin chosenas instances I mention anilin, toluidin,naphthylamin, phenylene-diamin, benzidin. This treatment can be effectedin the presence or absence of condensing agents, such as chlorid ofzinc, anilin hydrochlorate, boric acid, and so on. The heating iscontinued until the color of the melt nolonger changes. On cooling mynew coloring-matter separates out, usually in the crystalline form. Itis collected and dried. In this form my new coloring-matter is notgenerally usable directly for dyein g, being insufficiently soluble inwater, so that it has to be converted by sulfonating into the form ofsoluble sulfoacid.

The following examples will serve to illustrate the manner in which myinvention can be carried into effect and my new coloringmatter obtained.

Example 1: Production of new green coloring-matter from brominderivative of the alphylated amido-anthraquinone from1.5-dinitro-anthraquinone and aniZin.Mix about ten (10) parts of thesaid halogen derivative, which may have been obtained, for instance, asdescribed in Example 2 of the aforesaid application for Letters Patentof even date herewith, with about one hundred (100) parts of anilin.Stir the mixture and heat it while stirring until it boils. The melt isat first of a red color, but changes slowlyto violet, blue, and finallyto green. After boiling for about four hours, when no further change inthe color of the melt can be noticed, allow the melt to cool. Thecoloring-matter separates out in finely-crystalline form. In this formthe coloring-matter is a blue powder. In order to render it capable ofuse for dyeing, it is converted into the form of its soluble sulfoacid.

In the above example ten (10) parts of anilin salt might be added to actas condensing agent. The reaction then proceeds more quickly withoutaltering the nature of the product obtained.

In Example 1 the anilin can be replaced by para-toluidin and a similarproduct obtained. In working up this product the melt, after it iscooled, may be warmed up once more, in

order that the para-toluidin may melt, so

that the coloring-matter can be separated from it by filtering. Ifdesired, the coloringmatters can be precipitated from their melts bytreating with acids, but the products obtained thus are somewhat lesspure.

Example 2: Production of a new coloringmatter from the bromin derivativeof the alphyl-amido-anthraquinone obtained from 1.5-dinitro-anthraquinone and para-toluidin by condensation withpara-totuidin in the presence of a diZuent.Mix together about ten (10)parts of the said halogen derivative and about thirty (30) parts ofpara-toluidin and add the mixture to about two hundred (200) parts ofmelted naphthalene. Raise the temperature of the mixture until it boils.The formation of coloring-matter begins, as can be seen from the changein color of the melt from red to blue and finally to green. Allow themelt to cool and extract with alcohol. In this way the coloring-matteris separated from any excess of para-toluidin and from the naphthalene.The coloring-matter thus obtained is in the insoluble form and must besulfonated' to convert it into the form readily applicable for dyeing.

Example 8: Production of new coloringmatter from alphylatedamido-anthraquinone obtained from 1.fi-(lin/ifro-anflzruquinone andbenz'idia by condensation w t/71. (m'172'n.Mix together about ten (10)parts of the said halogen derivative and one hundred (100) parts ofanilin. Heat the mixture until it boils and maintain at this temperatureuntil the melt is green and shows no further change of color. Allow themelt to cool, and the coloring-matterseparates out in the crystallineform. Collect in any suitable manner.

The chlorin substitution products of the alphyl-amido-anthraquinones,theproduction of which is also described in the specification of even dateherewith, can also be used in the same way. It is only necessary thatthe correspondin quantity of the chlor derivative be used in the aboveexamples instead of the broinin derivative. The products obtained arefor practical purposes identical.

My new coloring-matters obtained according to this invention are all inthe unsulfonated form, while in the form of powder darkgreen in color,they frequently show crystalline structure. They are with difficultysoluble or not at all soluble in water and in alcohol, more easilysoluble in benzene, nitro-benzene, and anilin, giving blue-green to bluesolutions. On treating them with the usual sulfonating agents, such asconcentrated sulfuric acid, fuming sulfuric acid, chlorhydrin-sulfuricacid, mixtures of sulfuric acid and boracic acid or meta-phosphoricacid, with or without the addition of kieselguhr, &c., they are readilyconverted into sulfoacids. These are readily soluble in hot water,giving a green solution, which is hardly changed in color by theaddition of alkali. They dye unmordanted wool and wool mordanted withchrome, yielding green shades, which possess an excellent degree offastness to light.

I add further examples for the conversion of my new coloring-mattersinto their soluble form of sulfoacids:

Example 4.: SuZfbnu/ioa of the product of Erantple 1.l\lix about ten(10) parts of the product obtained according to Example 1 in the form ofthe dry powder with one hundred (100) parts of monohydrate sulfuricacid. Stir the mixture from time to time and maintain the temperature atabout 40 centigrade. Continue this treatment till a test portion isfully soluble in water. Pour the melt into water and precipitate thecoloring-matter with common salt or chlorid of potash. My newcoloring-matter in the form thus obtained is readily soluble in hotWater, giving a green solution, which is hardly changed by the additionof alkali.

Ercmple Sulfonation of the product obtained when using para-toluidiln inExample 1, and a mixture offitming sulfuric acid and boracz'c acid.--Mixtogether about ten (10) parts of the said insoluble coloring-matterobtained according to Example 1 with about ten (10) parts of boracieacid and one hundred (100) parts of fuming sulfuric acid containingabout five percent. free anhydride ($0 Heat the mixture to a temperatureof about 100 centigrade, until the coloring-matter is soluble in water.lVork up the coloring-matter in the manner described in Example a.

Now what I claim is- 1. The process for the production of greencoloring-matters of the anthracene series by heating theherein-described halogen derivatives of alphylatcd amido-anthraquinoneswith the herein-described primary aromatic amins, substantially ashercinbefore described.

2. As a newarticle of manufacture the green coloring-matters of theanthracene series which can be obtained from the herein-describedhalogen derivatives of alphylatcd amido-anthraquinones and a primaryaromatic amin and which in the unsulfonated form are with difficulty ornot at all soluble in water and in alcohol, more easily soluble inbenzene, nitrobenzene and anilin and in the sulfonated form are readilysoluble in hot water giving green solutions, which are hardly changed incolor by the addition of alkali.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

OSCAR BALLY.

Witnesses:

EnNEs'r F. Eni-umnnr, .T. L. IlElNKE.

